Method of preparing ethylene-α-olefin-diene copolymer

ABSTRACT

The present invention relates to a method of preparing an ethylene-α-olefin-diene copolymer and an ethylene-α-olefin-diene copolymer prepared thereby, by using a transition metal compound based on a cyclopenta[b]fluorenyl group as a catalyst.

TECHNICAL FIELD

The present invention relates to a method of preparing anethylene-α-olefin-diene copolymer and an ethylene-α-olefin-dienecopolymer prepared thereby, and more particularly to a method ofpreparing an ethylene-α-olefin-diene copolymer and anethylene-α-olefin-diene copolymer prepared thereby, by using atransition metal compound based on a cyclopenta[b]fluorenyl group as acatalyst.

BACKGROUND ART

In the prior art, so-called Ziegler-Natta catalyst consisting of atitanium or vanadium compound as a primary catalyst component and analkylaluminum compound as cocatalyst component have been generally usedfor preparing ethylene homopolymers or copolymers of ethylene andα-olefin. Although a Ziegler-Natta catalytic system exhibits highactivity on ethylene polymerization, the catalytic system hasdisadvantages in that molecular weight distribution of the producedpolymer is broad due to non-uniform catalyst activation point, andespecially, composition distribution thereof is not uniform in thecopolymers of ethylene and α-olefin.

Recently, so-called metallocene catalytic systems consisting of ametallocene compound of Group 4 transition metal in the Periodic Tableof Elements, such as titanium, zirconium and hafnium, andmethylaluminoxane as a cocatalyst have been developed. The metallocenecatalytic system is a homogeneous catalyst having a mono-modal catalystactivation point, and thus, can provide prepare polyethylene havingnarrower molecular weight distribution and more homogenous compositiondistribution as compared with the existing Ziegler-Natta catalystsystem. For example, European Patent Laid-Open Publication Nos. 320,762and 372,632; Japanese Patent Laid-Open Publication Nos. Sho 63-092621,Hei 02-84405 and Hei 03-2347 reported that ethylene may be polymerizedwith high activity by activating metallocene compounds such as Cp₂TiCl₂,Cp₂ZrCl₂, Cp₂ZrMeCl, Cp₂ZrMe₂, ethylene(IndH₄)₂ZrCl₂ by usingmethylaluminoxane as a cocatalyst, to prepare polyethylene having amolecular weight distribution (Mw/Mn) in the range from 1.5 to 2.0.However, it is difficult to obtain high-molecular weight polymers byusing the above catalytic system, and further, when solutionpolymerization executed at a high temperature of 100° C. or higher isemployed, polymerizing activity abruptly decreases and β-dehydrogenationis predominant. Therefore, the system has been known to be not suitablefor preparing high-molecular weight polymers having a weight averagemolecular weight (Mw) of 100,000 or more.

Meanwhile, there was reported so-called geo-restrictive non-metallocenebased catalysts (also referred to as single activation point catalysts)where the transition metals are linked in a ring type, as catalysts forpreparing high-molecular weight polymers with high catalytic activity inethylene homopolymerization or copolymerization of ethylene and α-olefinin the solution polymerization conditions. European Patent Nos. 0416815and 0420436 suggest an example where amide group is linked to onecyclopentadiene ligand in a ring type, and European Patent No. 0842939shows an example of the catalyst where phenol-based ligand as anelectron donor compound is linked to cyclopentadiene ligand in a ringtype. This geo-restrictive catalyst may remarkably improve reactivitywith higher α-olefins due to lowered sterical hinderance effect of thecatalyst itself, but has many difficulties in the commercial usethereof. Therefore, it has been important to secure more competitivecatalytic systems in requiring commercialized catalysts based oneconomical feasibility, that is, excellent high-temperature activity,excellent reactivity with higher α-olefins, and capability to preparehigh-molecular weight polymers.

DISCLOSURE OF INVENTION Technical Problem

In order to overcome the problems of the prior art, the presentinventors conducted extensive studies, and found that a transition metalcompound having a structure where a Group 4 transition metal in thePeriodic Table of Elements as a core metal is linked with acyclopenta[b]fluorenyl group that has a rigid plane structure eventhough it is not in a hetero ring; has abundant electrons widelynon-localized; and allows a substituent contributing to improvement insolubility and performance to be easily inducible at position 9 thereof,via an amido group substituted with a silyl group was advantageous inobtaining high-efficiency and high-molecular weight polymers inpolymerization of an ethylene-α-olefin-diene copolymer, and thus,completed the present invention.

An object of the present invention is to provide a method of preparingan ethylene-1-olefin-diene copolymer by using a transition metalcompound based on a cyclopenta[b]fluorenyl group as a catalyst.

Another object of the present invention is to provide anethylene-α-olefin-diene copolymer prepared by the method.

Solution to Problem

An aspect of the present invention for achieving the above objectsprovides a method of preparing an ethylene-α-olefin-diene copolymer byusing a transition metal compound based on a cyclopenta[b]fluorenylgroup represented by Chemical Formula 1 below. More specifically, atransition metal compound having a structure where a Group 4 transitionmetal in the Periodic Table of Elements as a core metal is linked with acyclopenta[b]fluorenyl group that has a rigid plane structure eventhough it is not in a hetero ring; has abundant electrons widelynon-localized; and allows a substituent contributing to improvement insolubility and performance to be easily inducible at position 9 thereof,via an amido group substituted with a silyl group, to thereby have anadvantageous structure in obtaining high-efficiency and high-molecularweight ethylene-α-olefin-diene copolymers, is used as a primarycatalyst.

In Chemical Formula 1, M is a Group 4 transition metal in the PeriodicTable of Elements;

n is an integer of 1 or 2, each R₁ may be the same or different when nis 2;

R₁ is hydrogen, (C1-C50)alkyl, halo(C1-C50)alkyl, (C3-C50)cycloalkyl,(C6-C30)aryl, (C6-C30)aryl(C1-C50)alkyl,((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl, —NR^(a)R^(b),—SiR^(c)R^(d)R^(e), or 5- through 7-membered N-heterocycloalkylcontaining at least one nitrogen atom;

R₂ and R₃ each are independently hydrogen, (C1-C50)alkyl,(C1-C50)alkoxy, halo(C1-C50)alkyl, (C3-C50)cycloalkyl, (C6-C30) aryl,(C6-C30)aryloxy, (C1-C50)alkyl(C6-C30)aryloxy,(C6-C30)aryl(C1-C50)alkyl, ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl,—NR^(a)R^(b) or —SiR^(c)R^(d)R^(e);

R₄, R₅, R₁₀, R₁₁ and R₁₂ each are independently (C1-C50)alkyl,halo(C1-C50)alkyl, (C3-C50)cycloalkyl, (C6-C30)aryl,(C6-C30)aryl(C1-C50)alkyl, ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl,—NR^(a)R^(b), or —SiR^(c)R^(d)R^(e), and R₁₁ and R₁₂ may be linked via(C4-C7)alkylene to form a ring;

R₆, R₇, R₈ and R₉ each are independently hydrogen, (C1-C50)alkyl,halo(C1-C50)alkyl, (C3-C50)cycloalkyl, (C1-C50)alkoxy, (C6-C30)aryl,(C6-C30)aryl(C1-C50)alkyl, ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl,(C6-C30)aryloxy, (C1-C50)alkyl(C6-C30)aryloxy, N-carbazolyl,—NR^(a)R^(b), or —SiR^(c)R^(d)R^(e), or may be linked to an adjacentsubstituent via (C1-C5)alkylene to form a ring, and at least one —CH₂—of the alkylene may be substituted by a hetero atom selected from —O—,—S—, and —NR′—, and the alkylene may be further substituted with(C1-C50)alkyl;

aryl of R₁ to R₁₂ may be further substituted with at least onesubstituent selected from the group consisting of (C1-C50)alkyl,halo(C1-C50)alkyl, (C1-C50)alkoxy, (C6-C30)aryloxy, (C6-C30)aryl,(C1-C50)alkyl(C6-C30)aryl, and (C6-C30)aryl(C1-C50)alkyl;

R′ and R^(a) to R^(e) each are independently (C1-C50)alkyl or(C6-C30)aryl; and

X₁ and X₂ each are independently halogen, (C1-C50)alkyl,(C2-C50)alkenyl, (C3-C50)cycloalkyl, (C6-C30)aryl,(C6-C30)aryl(C1-C50)alkyl, ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl,(C1-C50)alkoxy, (C6-C30)aryloxy, (C1-C50)alkyl(C6-C30)aryloxy,(C1-C50)alkoxy(C6-C30)aryloxy, (C1-C50)alkylidene, or an anion ordianion ligand consisting of 60 or less atoms containing N, P, O, S, Si,and halogen, except hydrogen, provided that one of X₁ and X₂ is adianion ligand, the other is ignored.

An example of the transition metal compound based on thecyclopenta[b]fluorenyl group represented by Chemical Formula 1 above mayinclude a transition metal compound represented by Chemical Formula 2 or3 below:

In Chemical Formulas 2 and 3, M, R₂ to R₁₂, X₁ and X₂ has the samedefinition in Chemical Formula 1; R₂₁ and R₂₂ each are independentlyhydrogen, (C1-C50)alkyl, halo(C1-C50)alkyl, (C3-C50)cycloalkyl,(C6-C30)aryl, (C6-C30)aryl(C1-C50)alkyl,((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl, —NR^(a)R^(b),—SiR^(c)R^(d)R^(e), or 5- through 7-membered N-heterocycloalkylcontaining at least one nitrogen atom; aryl of R₁ may be furthersubstituted with at least one substituent selected from the groupconsisting of halogen, (C1-C50)alkyl, halo(C1-C50)alkyl, (C1-C50)alkoxy,(C6-C30)aryloxy, (C6-C30)aryl, (C1-C50)alkyl(C6-C30)aryl, and(C6-C30)aryl(C1-C50)alkyl; and R^(a) to R^(e) each are independently(C1-C50)alkyl or (C6-C30)aryl.

Another aspect of the present invention for achieving the above objectsprovides an ethylene-α-olefin-diene copolymer prepared by the method ofpreparing an ethylene-α-olefin-diene copolymer, by using a transitionmetal catalyst composition containing the transition metal compound.

Hereinafter, the present invention will be described in more detail.

The Group 4 transition metal in the Periodic Table of Elements, M, ispreferably titanium (Ti), zirconium (Zr), or hafnium (Hf).

The term “alkyl” described herein includes a straight chain type or abranched chain type.

The term “aryl” described herein is an organic radical derived fromaromatic hydrocarbon by the removal of one hydrogen atom, and mayinclude a single ring or a fused ring containing, properly 4 to 7 ringatoms, and preferably 5 or 6 ring atoms. Specific examples thereofinclude phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl,triphenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl,or the like, but are not limited thereto.

For example, (C1-C50)alkyl may be methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl,n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl,n-pentadecyl, n-octadecyl, n-icosyl, or n-docosyl; (C3-C50)cycloalkylmay be, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, cyclodecyl, or cyclododecyl; (C6-C30)aryl or(C1-C50)alkyl(C6-C30)aryl may be, for example, phenyl, 2-tolyl, 3-tolyl,4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl,3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl,2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl,2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl,2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl,n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl,tert-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl,n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl,biphenyl, fluorenyl, triphenyl, naphthyl, or anthracenyl;(C6-C30)aryl(C1-C50) alkyl or ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkylmay be, for example, benzyl, (2-methylphenyl)methyl,(3-methylphenyl)methyl, (4-methylphenyl)methyl,(2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl,(2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl,(3,4-dimethylphenyl)methyl, (4,6-dimethylphenyl)methyl,(2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl,(2,3,6-trimethyl-phenyl)methyl, (3,4,5-trimethylphenyl)methyl,(2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl,(2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl,(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl, or anthracenylmethyl; and(C1-C50)alkoxy may be, for example, methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy,neopentyloxy, n-hexyloxy, n-octyloxy, n-dodecyloxy, n-pentadecyloxy, orn-eicosyloxy.

Preferably, each R₁ is independently hydrogen, methyl, ethyl, n-propyl,isopropyl, n-butyl, phenyl, naphthyl, biphenyl, 2-isopropylphenyl,3,5-xylyl, 2,4,6-trimethylphenyl, benzyl, dimethylamino, or pyrrolidino;

preferably, R₂ and R₃ are independently hydrogen, methyl, ethyl,n-propyl, isopropyl, n-butyl, phenyl, naphthyl, biphenyl,2-isopropylphenyl, 3,5-xylyl, 2,4,6-trimethylphenyl, benzyl, methoxy,ethoxy, isopropoxy, phenoxy, 4-tert-butylphenoxy, or naphthoxy;

preferably, R₄ and R₅ each are independently methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, 2-methylbutyl, sec-butyl, tert-butyl,n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl,n-tetradecyl, n-hexadecyl, n-pentadecyl, n-octadecyl, n-icosyl,n-docosyl, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl,2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl,2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl,3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, biphenyl, fluorenyl, triphenyl, naphthyl,anthracenyl, benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl,(4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl,(2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl,(2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl,(4,6-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl,(2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl,(3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl,(2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl,(2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl,(ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl,(n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl, anthracenylmethyl,4-methoxyphenyl, 3,4-dimethoxyphenyl, or4-(hexyloxy)-3,5-dimethylphenyl;

preferably, R₆ to R₉ each are independently hydrogen, methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, 2-methylbutyl, sec-butyl,tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl,n-dodecyl, n-pentadecyl, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl,2,4-xylyl, 2,5-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl,trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl,3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, biphenyl, fluorenyl,2,7-di-tert-butyl-9-p-tolyl-9H-fluoren-9-yl, triphenyl, naphthyl,anthracenyl, benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl,(4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl,(2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl,(2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl,(4,6-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl,(2,3,5-trimethylphenyl)methyl, (2,3,6-trimethyl-phenyl)methyl,(3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl,(2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl,(2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl,(ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl,(n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl, anthracenylmethyl,4-methoxyphenyl, 3,4-dimethoxyphenyl, methoxy, ethoxy, isopropoxy,n-butoxy, n-hexyloxy, 2-methylbutyl, phenoxy, 4-tert-butylphenoxy,naphthoxy, trimethylsilyl, triphenylsilyl, dimethylamino, diphenylamino,or 9H-carbazol-9-yl, or may be linked to an adjacent substituent via

to form a ring, L₁ and L₂ each are independently —O—, —S—, or —NR′—[each R′ is independently (C1-C50)alkyl or (C6-C30)aryl], R₃₁ to R₃₄each, independently, have the same definition as R₄ and R₅, and morepreferably, hydrogen, methyl, or n-tetradecyl;

preferably, R₁₁ and R₁₂ each are independently methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, 2-methylbutyl, sec-butyl, tert-butyl,n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl,n-pentadecyl, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl,2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl,2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl,3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, biphenyl, fluorenyl, triphenyl, naphthyl,anthracenyl, benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl,(4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl,(2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl,(2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl,(4,6-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl,(2,3,5-trimethylphenyl)methyl, (2,3,6-trimethyl-phenyl)methyl,(3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl,(2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl,(2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl,(ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl,(n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-tetradecylphenyl)methyl, naphthylmethyl,anthracenylmethyl, 4-methoxyphenyl, or 3,4-dimethoxyphenyl, or R₁₁ andR₁₂ may be linked to each other via butylene or pentylene to form aring;

R₁₀ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,2-methylbutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl,n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl, cyclohexyl, phenyl,2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl,3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl,2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl,2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl,2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl,n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl,tert-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl,n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl,biphenyl, fluorenyl, triphenyl, naphthyl, anthracenyl, benzyl,(2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl,(2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl,(2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl,(3,4-dimethylphenyl)methyl, (4,6-dimethylphenyl)methyl,(2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl,(2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl,(2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl,(2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl,(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl, anthracenylmethyl,2-methoxyphenyl, or 3,4-dimethoxyphenyl.

In the definitions of substituents X₁ and X₂, examples of halogen atommay include fluorine, chlorine, bromine, and iodine atom; examples of(C1-C50)alkyl may include methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, n-octyl,n-decyl, n-dodecyl, n-pentadecyl, and n-eicosyl; examples of(C3-C50)cycloalkyl may include cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, and adamantyl; examples of (C6-C30)aryl mayinclude phenyl and naphthyl; examples of (C6-C30)aryl(C1-C50)alkyl or((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl may include benzyl,(2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl,(2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl,(2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl,(3,4-dimethylphenyl)methyl, (4,6-dimethylphenyl)methyl,(2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl,(2,3,6-trimethyl-phenyl)methyl, (3,4,5-trimethylphenyl)methyl,(2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl,(2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl,(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl, and anthracenylmethyl;examples of (C1-C50)alkoxy may include methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy,neopentyloxy, n-hexyloxy, n-octyloxy, n-dodecyloxy, n-pentadecyloxy, andn-eicosyloxy; examples of (C6-C30)aryloxy may include phenoxy,4-tert-butylphenoxy, or 4-methoxyphenoxy, the anion or dianion ligandconsisting of 60 or less atoms containing N, P, O, S, Si, and halogen,except for hydrogen may be —OSiR^(f)R^(g)R^(h), —SR^(i) [R^(f) to R^(i)each are independently (C1-C50)alkyl, (C6-C30)aryl, (C3-C50)cycloalkyl],—NR^(j)R^(k), or —PR^(l)R^(m) [R^(j) to R^(m) each are independently(C1-C50)alkyl, (C6-C30)aryl, (C6-C30)aryl(C1-C50)alkyl,(C3-C20)cycloalkyl, tri(C1-C50)alkylsilyl, or tri(C6-C30)arylsilyl].Examples of −OSiR^(f)R^(g)R^(h) may include trimethylsiloxy,triethylsiloxy, tri-n-propylsiloxy, triisopropylsiloxy,tri-n-butylsiloxy, tri-sec-butylsiloxy, tri-tert-butylsiloxy,tri-isobutylsiloxy, tert-butyldimethylsiloxy, tri-n-pentylsiloxy,tri-n-hexylsiloxy, or tricyclohexylsiloxy; examples of —NR^(j)R^(k) mayinclude dimethylamino, diethylamino, di-n-propylamino, diisopropylamino,di-n-butylamino, di-sec-butylamino, di-tert-butylamino, diisobutylamino,tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino,di-n-decylamino, diphenylamino, dibenzylamino, methylethylamino,methylphenylamino, benzylhexylamino, bis(trimethylsilyl)amino, orbis(tert-butyldimethylsilyl)amino; examples of —PR^(l)R^(m) may includedimethylphosphine, diethylphosphine, di-n-propylphosphine,diisopropylphosphine, di-n-butylphosphine, di-sec-butylphosphine,di-tert-butylphosphine, diisobutylphosphine,tert-butylisopropylphosphine, di-n-hexylphosphine, di-n-octylphosphine,di-n-decylphosphine, diphenylphosphine, dibenzylphosphine,methylethylphosphine, methylphenylphosphine, benzylhexylphosphine,bis(trimethylsilyl)phosphine, and bis(tert-butyldimethylsilyl)phosphine;examples of —SR^(i) may include methylthio, ethylthio, propylthio,isopropylthio, butylthio, or isopentylthio.

X₁ and X₂ each are independently fluorine, chlorine, bromine, methyl,ethyl, isopropyl, amyl, benzyl, methoxy, ethoxy, isopropoxy,tert-butoxy, phenoxy, 4-tert-butylphenoxy, trimethylsiloxy,tert-butyldimethylsiloxy, dimethylamino, diphenylamino,dimethylphosphino, diethylphosphino, diphenylphosphino, ethylthio, orisopropylthio.

The above transition metal compound may be selected from compounds ofthe structures below, but is not limited thereto:

M is Ti, Zr, or Hf; and X₁ and X₂ each have the same definition asdefined in Chemical Formula 1 above.

Meanwhile, in order to be an active catalyst component to be used forpreparing an ethylene-α-olefin-diene copolymer, the transition metalcompound of Chemical Formula 1 above may preferably act together with,as a cocatalyst, an aluminum compound, a boron compound, or a mixturethereof, which can extract an X₁ or X₂ ligand from the transition metalcompound to cationize the core metal and act as a counterion having weakbond strength, that is, an anion.

That is, the transition metal catalyst composition may, preferably,further contain a cocatalyst selected from an aluminum compound, a boroncompound, or a mixture thereof, as well as the transition metal compoundof Chemical Formula 1.

The boron compound usable as the cocatalyst in the present invention hasbeen known in U.S. Pat. No. 5,198,401, and may be selected from boroncompounds represented by Chemical Formulas 4 to 6 below:B(R⁴¹)₃  [Chemical Formula 4][R⁴²]⁺[B(R⁴¹)₄]⁻  [Chemical Formula 5][(R⁴³)_(p)ZH]⁺[B(R⁴¹)₄]⁻  [Chemical Formula 6]

In Chemical Formulas 4 to 6, B is a boron atom;

R⁴¹ is phenyl, and the phenyl may be further substituted with 3 to 5substituents selected from a fluorine atom, (C1-C50)alkyl substituted orunsubstituted with a fluorine atom, or (C1-C50)alkoxy substituted orunsubstituted with a fluorine atom;

R⁴² is (C5-C7)aromatic radical or (C1-C50)alkyl(C6-C20)aryl radical,(C6-C30)aryl(C1-C50)alkyl radical, for example, triphenylmethyl radical;

Z is a nitrogen or phosphorus atom;

R⁴³ is (C1-C50)alkyl radical, or anilinium radical substituted with anitrogen atom and two (C1-C50)alkyl groups; and p is an integer of 2 or3.

Preferable examples of the boron based cocatalyst may includetris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane,tris(2,3,4,5-tetrafluorophenyl)borane,tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane,phenylbis(pentafluorophenyl)borane, tetrakis(pentafluorophenyl)borate,tetrakis(2,3,5,6-tetrafluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,tetrakis(2,2,4-trifluorophenyl)borate,phenylbis(pentafluorophenyl)borate, andtetrakis(3,5-bistrifluoromethylphenyl)borate. In addition, certaincompounded examples thereof may include ferroceniumtetrakis(pentafluorophenyl)borate, 1,1′-dimethylferroceniumtetrakis(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)borate,triphenylmethyl tetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bistrifluoromethylphenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bistrifluoromethylphenyl)borate, diisopropylammoniumtetrakis(pentafluorophenyl)borate, dicyclohexylammoniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, and tri(dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate. Among them, preferable areN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(pentafluorophenyl)borate, and tris(pentafluorophenyl)borane.

In the present invention, the aluminum compounds usable as thecocatalyst may selected from aluminoxane compounds of Chemical Formula 7or 8, organic aluminum compounds of Chemical Formula 9, or organicaluminum hydrocarbyloxide compounds of Chemical Formula 10 or 11:(—Al(R⁵¹)—O—)_(m)  [Chemical Formula 7](R⁵¹)₂Al—(—O(R⁵¹)—)_(q)—(R⁵¹)₂  [Chemical Formula 8](R⁵²)_(r)Al(E)_(3-r)  [Chemical Formula 9](R⁵³)₂AlOR⁵⁴  [Chemical Formula 10]R⁵³Al(OR⁵⁴)₂  [Chemical Formula 11]

In Chemical Formulas 7 to 11, R⁵¹ is (C1-C50)alkyl, preferably methyl orisobutyl; m and q each are independently an integer of 5 to 20; R⁵² andR⁵³ each are independently (C1-C50)alkyl; E is a hydrogen or halogenatom; r is an integer of 1 to 3; and R⁵⁴ is (C1-C50)alkyl or(C6-C30)aryl.

Specific examples of the aluminum compound may include aluminoxanecompounds, such as methylaluminoxane, modified methylaluminoxane,tetraisobutylaluminoxane; organic aluminum compounds, such astrialkylaluminum including trimethylaluminum, triethylaluminum,tripropylaluminum, triisobutylaluminum, and trihexylaluminum;dialkylaluminum chloride including dimethylaluminum chloride,diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminumchloride, and dihexylaluminum chloride; alkylaluminum dichlorideincluding methylaluminum dichloride, ethylaluminum dichloride,propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminumdichloride; and dialkylaluminum hydride including dimethylaluminumhydride, diethylaluminum hydride, dipropylaluminum hydride,diisobutylaluminum hydride and dihexylaluminum hydride. Among them,preferable is trialkylaluminum, and more preferable are triethylaluminumand triisobutylaluminum.

In the transition metal catalyst composition containing both of theprimary catalyst and the cocatalyst, the transition metal compound asthe primary catalyst and the cocatalyst have preferably a molar ratio oftransition metal (M):boron atom (B):aluminum atom (Al) in the range of1:0˜100:1˜2,000, and more preferably 1:0.5˜5:10˜500. The above ratioenables the preparation of the ethylene-α-olefin-diene copolymer, andthe range of the ratio may be varied depending on purity of reaction.

The method of preparing an ethylene-α-olefin-diene copolymer by usingthe transition metal catalyst composition may be carried out bycontacting the transition metal catalyst, cocatalyst, and ethylene,α-olefin comonomers, and diene monomer, in the presence of appropriateorganic solvent. Here, the transition metal compound (primary catalyst)and the cocatalyst components may be separately fed to the reactor, orthose components may be mixed in advance and then fed to the reactor.The mixing conditions, such as the order of feeding, temperature, orconcentration, are not particularly restricted.

Preferable examples of organic solvents usable in the preparing methodmay include (C3-C20) hydrocarbon, and specific examples thereof mayinclude butane, isobutane, pentane, hexane, heptane, octane, isooctane,nonane, decane, dodecane, cyclohexane, methylcyclohexane, benzene,toluene, xylene, and the like.

The ethylene-α-olefin-diene copolymer prepared according to the presentinvention is characterized by having Mooney viscosity (ASTM D1646-94,ML1+4@125° C.) of the entire copolymer in the range of 1 to 250, andcontaining 30 to 85 wt % of ethylene, 1 to 15 wt % of diene, and therest of α-olefin.

Specifically, a pressure in a reactor for preparing theethylene-α-olefin-diene copolymer is 1˜1000 atm, and more preferably6˜150 atm. Also, effectively, the polymerization reaction temperaturemay be 25° C.˜200° C., and preferably 50° C.˜180° C.

As an α-olefin comonomer used in the present invention, straight orbranched chain (C3-C18) α-olefin, (C5-C20) cycloolefin, styrene, orstyrene derivatives may be used. Preferable examples of straight orbranched chain (C3-C18) α-olefin may include propylene, 1-butene,1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decease,1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, andthe like; preferable examples of (C5-C20) cycloolefin may includecyclopentene, cyclohexene, norbornene, phenylnorbornene, and the like;and preferable examples of styrene and derivatives thereof may includestyrene, α-methylstyrene, p-methylstyrene, 3-chloromethylstyrene, andthe like.

The diene monomer used in the present invention has two double bonds,and straight and branched chain C4˜C20 diolefin or C5˜C20 cyclodiolefinmay be used therefor. Preferable examples of straight or branched chainC4˜C20 diolefin may include 1,3-butadiene, 1,4-pentadiene,2-methyl-1,3-butadiene, 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene,1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,7-nonadiene,1,8-nonadiene, 1,8-decadiene, 1,9-decadiene, 1,12-tetradecadiene,1,13-tetradecadiene, 3-methyl-1,4-hexadiene, 3-methyl-1,5-hexadiene,3-ethyl-1,4-hexadiene, 3-ethyl-1,5-hexadiene,3,3-dimethyl-1,4-hexadiene, 3,3-dimethyl-1,5-hexadiene, and the like;and preferable examples of C5˜C20 cyclodiolefin may includecyclopentadiene, cyclohexadiene, 5-vinyl-2-norbornene,2,5-norbornadiene, 7-methyl-2,5-norbornadiene,7-ethyl-2,5-norbornadiene, 7-propyl-2,5-norbornadiene,7-butyl-2,5-norbornadiene, 7-phenyl-2,5-norbornadiene,7-hexyl-2,5-norbornadiene, 7,7-dimethyl-2,5-norbornadiene,7-methyl-7-ethyl-2,5-norbornadiene, 7-chloro-2,5-norbornadiene,7-bromo-2,5-norbornadiene, 7-fluoro-2,5-norbornadiene,7,7-dichloro-2,5-norbornadiene, 1-methyl-2,5-norbornadiene,1-ethyl-2,5-norbornadiene, 1-propyl-2,5-norbornadiene,1-butyl-2,5-norbornadiene, 1-chloro-2,5-norbornadiene,1-bromo-2,5-norbornadiene, 5-isopropyl-2-norbornene,5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB),5-ethylidene-2-norbornene (ENB), and the like.

As described above, ethylene/propylene/diene (EPDM) elastomer can beexcellently prepared by using the catalyst of the present invention.Especially, since high-price diene is easily injected, EPDM productshaving Mooney viscosity (ASTM D1646-94, ML1+4@ 125° C.) adjusted in therange of 1 to 250, and preferably 10 to 200 can be easily manufacturedin an economical manner.

In addition, when the ethylene-α-olefin-diene copolymer according to thepresent invention is prepared, hydrogen may be used as a molecularweight regulator in order to regulate the molecular weight.

Generally, when solution polymerization is carried out at a hightemperature as described above, the catalyst may be transformed ordeteriorated due to the increase in temperature, which may causeactivity of the catalyst to be lowered, and thus, polymers havingdesired physical properties can not be obtained. However, since thecatalyst composition proposed by the present invention is present in ahomogeneous state in the polymerization reactor, the catalystcomposition may be preferably employed in a solution polymerizationprocess carried out at a temperature higher than the melting point ofthe corresponding polymer. However, as disclosed by U.S. Pat. No.4,752,597, the transition metal compound and cocatalyst may be supportedon a porous metal oxide supporter, to thereby be used for slurrypolymerization or a gas phase polymerization process, as a heterogeneouscatalyst composition.

Advantageous Effects of Invention

As set forth above, in the method of preparing theethylene-α-olefin-diene copolymer according to the present invention,the transition metal compound based on a cyclopenta[b]fluorenyl group isused as a polymerization catalyst, and thus, ethylene-α-olefin-dienecopolymers having a high diene content, a high conversion ratio, andhigh Mooney viscosity can be prepared under the high-temperature (120°C. or higher) polymerization conditions at a high yield. Further, thecatalyst composition containing the transition metal compound can beeasily prepared at a high synthesis yield in an economical manner.Further, the transition metal compound or the catalyst compositionaccording to the present invention can have excellent copolymerizationreactivity with other olefins while maintaining high catalytic activityeven at high temperature due to excellent thermal stability thereof andallow the preparation of high-molecular weight polymers at a high yield,resulting in higher commercial practicability as compared with thealready known metallocene and non-metallocene based single activationpoint catalysts.

MODE FOR THE INVENTION

Hereinafter, the embodiments of the present invention will be describedin detail with reference to accompanying Examples, which are notintended to restrict the scope of the invention.

Unless mentioned otherwise, all experiments for synthesizing ligands andcatalysts were carried out under nitrogen atmosphere by using standardSchlenk or glove-box techniques. The organic solvents used in thereaction were subjected to reflux over sodium metal and benzophenone tothereby remove moisture, and then distilled immediately before use.¹H-NMR analyses of the synthesized ligands and catalysts were performedby using Bruker 500 MHz at room temperature.

Before use, n-heptane, as solvent for polymerization, was passed througha tube filled with molecular sieve 5 Å and activated alumina, andbubbled by high-purity nitrogen, to thereby sufficiently removemoisture, oxygen and other catalyst poison materials. The polymerizedpolymers were analyzed by the measurement methods described below.

1. Melt flow index (MI)

Measurement was conducted according to ASTM D 2839.

2. Density

Measurement was conducted by using density gradient tubes, according toASTM D 1505.

3. Melting temperature (Tm)

Measurement was conducted in the conditions of 2^(nd) heating at a rateof 10° C./min under nitrogen atmosphere, by using Dupont DSC 2910.

4. Molecular weight and molecular weight distribution

Measurement was conducted at 135° C. at a rate of 1.0 mL/min in thepresence of 1,2,3-trichlorobenzene solvent, by using PL210 GPC equippedwith PL Mixed-BX2+preCol, and molecular weight was calibrated by usingPL polystyrene standards.

5. α-olefin content (wt %) in copolymer

Measurement was conducted by using 1,2,4-trichlorobenzene/C₆D₆ (7/3 byweight) mixture solvent at 120° C. in the ¹³C-NMR mode through BrukerDRX500 NMR spectrometer at 125 MHz. (Reference: Randal, J. C. JMS-Rev.Macromol. Chem. Phys. 1980, C29, 201)

The ratio of ethylene and α-olefin and the diene content in EPDMpolymers were quantified by using an infrared spectrometer.

Preparation Example 1 Preparation of Mixture of Complex 1 and Complex 2

Synthesis of 9,9-dihexyl-9H-fluorene

A 2000 mL round flask was charged with 9H-fluorene (50 g, 300.1 mmol)and potassium t-butoxide (77.0 g, 721.9 mmol), and then 700 mL of DMSOwas slowly injected thereto. 1-Bromohexane (119 g, 721.9 mmol) wasslowly added thereto from a dropping funnel under nitrogen atmosphere.The mixture was stirred at room temperature for 24 hours, and thereaction was terminated by addition of 500 mL of distilled water. Theorganic layer collected by extraction with n-hexane was dried overmagnesium sulfate, followed by removal of volatile materials, and thenpurified with n-hexane by using silica gel column chromatography,followed by drying and long-time storage at room temperature, to therebyobtain 90.0 g of 9,9-dihexyl-9H-fluorene (yield: 72.40%) as solid.

¹H-NMR (500 MHz, CDCl₃, ppm): δ 0.625-0.628 (m, 4H), 0.759-0.785 (m,6H), 1.050-1.125 (m, 12H), 1.953-1.983 (t, 4H), 7.293-7.340 (m, 6H),7.706-7.720 (d, 2H)

Synthesis of9,9-dihexyl-2-methyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one

A 2000 mL round flask was charged with 9,9-dihexyl-9H-fluorene (79 g,236.2 mmol) and 2-bromo-2-methylpropanoyl bromide (54.3 g, 236.2 mmol),and then dissolved with 600 mL of carbon disulfide inputted thereto.Then, the reactor was cooled with ice water. Under nitrogen atmosphere,aluminum trichloride (78.7 g, 590.4 mmol) was slowly added thereto inten lots over 2 hours. The mixture was stirred at room temperature for 8hours, and then the reaction was terminated by addition of 500 mL ofdistilled water, followed by washing 3 times with 500 mL of distilledwater. The organic layer was dried over magnesium sulfate, followed byremoval of volatile materials and drying, to thereby obtain 89.0 g of9,9-dihexyl-2-methyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one (yield:93.6%) as highly viscous oil.

¹H-NMR (500 MHz, CDCl₃, ppm): δ 0.601-0.627 (m, 4H), 0.741-0.774 (m,6H), 1.000-1.126 (m, 12H), 1.366-1.380 (d, 3H), 1.961-2.202 (m, 4H),2.789-2.801 (d, 2H), 3.445-3.498 (m, 1H), 7.375-7.383 (m, 3H), 7.731 (s,2H), 7.764-7.779 (d, 1H)

Synthesis of9,9-dihexyl-2-methyl-1,2,3,9-tetrahydrocyclopenta[b]fluoren-1-ol

In a 1000 mL round flask,9,9-dihexyl-2-methyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one (85 g,211.1 mmol) was dissolved in THF 400 mL and ethanol 400 mL, and thenstirred. Sodium borohydride (NaBH₄) (10 g, 265.0 mmol) was added to thereaction product in five lots, and then stirred for 12 hours. Theresultant mixture, after removal of solvent, was dissolved inethylacetate, and then washed with water three times. The organic layerwas dried over magnesium sulfate, followed by removal of volatilematerials and drying, to thereby obtain 82.0 g of9,9-dihexyl-2-methyl-1,2,3,9-tetrahydrocyclopenta[b]fluoren-1-ol (yield:96.0%) (two isomers), as highly viscous oil.

¹H-NMR (500 MHz, CDCl₃, ppm): δ 0.628-0.631 (m, 8H), 0.762-0.788 (m,12H), 1.109-1.136 (m, 24H), 1.198-1.212 (d, 3H), 1.314-1.327 (d, 3H),1.522-1.535 (d, 1H), 1.830-1.846 (d, 1H), 1.956-1.963 (m, 8H),2.323-2.352 (m, 1H), 2.525-2.572 (m, 1H), 2.628-2.655 (m, 1H),2.733-2.779 (m, 1H), 3.011-3.057 (m, 1H), 3.164-3.210 (m, 1H),4.783-4.812 (t, 1H), 5.052-5.077 (t, 1H), 7.289-7.380 (m, 8H), 7.525 (s,1H), 7.558 (s, 1H), 7.672-7.685 (d, 2H)

Synthesis of 9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluorene

In a 500 mL round flask,9,9-dihexyl-2-methyl-1,2,3,9-tetrahydrocyclopenta[b]fluoren-1-ol (80 g,197.7 mmol) and p-toluene sulfonic acid (0.2 g) were dissolved in 320 mLof toluene, and then water was completely removed under reflux withDean-Stark. The resultant material was cooled to room temperature, andthen an aqueous ammonium chloride solution (150 mL) and 200 mL ofdiethyl ether were injected thereto, followed by separation of theorganic layer. The organic layer collected by extracting the residuewith diethyl ether was dried over magnesium sulfate, followed by removalof volatile materials, and then purified by using silica gel columnchromatography tube, to thereby obtain 74.0 g of9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluorene (yield: 96.8%).

¹H-NMR (500 MHz, CDCl₃, ppm): δ 0.611-0.671 (m, 4H), 0.755-0.784 (m,6H), 1.041-1.140 (m, 12H), 1.943-1.976 (m, 4H), 2.200 (s, 3H), 3.373 (s,2H), 6.556 (s, 1H), 7.208-7.381 (m, 4H), 7.653-7.668 (d, 1H), 7.700 (s,1H)

Synthesis ofN-tert-butyl-1-(9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(9,9-dihexyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine

In a 500 mL round flask,9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluorene (40.0 g, 103.5mmol) was dissolved in 320 mL of diethyl ether, and then the temperaturewas lowered to −78° C. Then, n-butyllithium (2.5M hexane solution, 42mL) was slowly injected thereto, followed by stirring at roomtemperature for 12 hours. After volatile materials were removed byvacuum, 350 mL of n-hexane was added to the mixture to lower the reactortemperature to −78° C., followed by addition of dichlorodimethylsilane(40 g). The temperature was again raised to room temperature, followedby stirring for 24 hours, and then salts were removed through filtering.Then, volatile materials were removed by vacuum. The product was againinputted to a 500 mL round flask, and dissolved in 320 mL of diethylether. The temperature was lowered to −78° C., and tert-butylamine (22.7g, 310.4 mmol) was added thereto. The temperature was raised to roomtemperature, followed by stirring for 12 hours, and then volatilematerials were completely removed by vacuum. Then, 200 mL of n-hexanewas added to dissolve the resultant material, and salts were removedthrough filtering. The solvent was removed, to thereby obtain 48 g of amixture ofN-tert-butyl-1-(9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(9,9-dihexyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine(ratio=˜1:1), (yield: 88.9%), as viscous material.

¹H-NMR (500 MHz, C₆D₆, ppm): δ 0.132 (s, 3H), 0.177-0.198 (d, 6H), 0.270(s, 1H), 0.804-0.879 (m, 12H), 0.973-1.295 (m, 50H), 2.170-2.348 (m,14H), 3.398-3.428 (d, 2H), 6.745 (s, 2H), 7.337-7.434 (m, 6H),7.518-7.908 (m, 6H)

Synthesis of(t-butylamido)dimethyl(9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl(Complex 1) and(t-butylamido)dimethyl(9,9-dihexyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)silanetitanium(IV)(Complex 2)

In a 500 mL round flask, a mixture ofN-tert-butyl-1-(9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)1,1-dimethylsilanamineandN-tert-butyl-1-(9,9-dihexyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1-yl)-1,1-dimethylsilanamine(ratio=˜1:1) (8.64 g, 16.75 mmol) was dissolved in 130 mL of diethylether, and then the temperature was lowered to −78° C. Then,methyllithium (1.5M diethyl ether solution, 49.4 mL) was slowly injectedthereto. The temperature was raised to room temperature, followed bystirring for 12 hours, to prepare lithium salt. In addition, in a drybox, TiCl₄ (16.75 mmol) and 150 mL of anhydrous n-hexane were inputtedto a 500 mL round flask, and then the temperature was lowered to −78° C.Then, the prepared lithium salt was slowly added thereto. Thetemperature was again raised to room temperature, followed by stirringfor 4 hours, and the solvent was removed by vacuum. The resultantmaterial was dissolved in n-hexane, and then the filtrate was extractedthrough filtering. Again, the solvent was removed by vacuum, to therebyobtain 8.1 g of a mixture of Complex 1 and Complex 2 (ratio ofapproximately 1:1), as solid.

¹H-NMR (500 MHz, C₆D₆, ppm): δ 0.079-0.091 (d, 6H), 0.623-0.645 (d, 6H),0.813-1.336 (m, 56H), 1.601-1.619 (d, 18H), 2.071-2.514 (m, 14H),7.025-7.035 (d, 2H), 7.330-8.099 (m, 12H)

Preparation Example 2 Preparation of Mixture of Complex 3 and Complex 4

Synthesis of 9,9-dimethyl-9H-fluorene

A 2000 mL round flask was charged with 9H-fluorene (50 g, 300.1 mmol)and potassium t-butoxide (77.0 g, 721.9 mmol), and then 700 mL of DMSOwas slowly injected thereto. Under nitrogen atmosphere, iodomethane(113.5 g, 800 mmol) was slowly dropped through a dropping funnel whilethe reactor temperature was maintained at 10° C. or lower. The mixturewas stirred at room temperature for 24 hours, and the reaction wasterminated by addition of 500 mL of distilled water. The organic layercollected by extraction with n-hexane was dried over magnesium sulfate,followed by removal of volatile materials, and then purified withn-hexane by using silica gel column chromatography tube, followed bydrying, to thereby obtain 47.5 g of 9,9-dimethyl-9H-fluorene (yield:81.50%) as white solid.

¹H-NMR (500 MHz, CDCl₃, ppm): δ 1.547 (s, 6H), 7.368-7.393 (t, 4H),7.488-7.499 (d, 2H), 7.777-7.791 (d, 2H)

Synthesis of 2,9,9-trimethyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one

A 2000 mL round flask was charged with 9,9-dimethyl-9H-fluorene (50 g,257.4 mmol) and 2-bromo-2-methylpropanoyl bromide (61.0 g, 265.1 mmol),and then dissolved with 700 mL of carbon disulfide inputted thereto.Then, the reactor was cooled with ice water. Under nitrogen atmosphere,aluminum trichloride (85.8 g, 643.4 mmol) was slowly added thereto inten lots over 2 hours. The mixture was stirred at room temperature for 8hours, and then the reaction was terminated by addition of 500 mL ofdistilled water. The resultant mixture was diluted by adding 500 mL ofmethyl chloride and washed with 500 mL of distilled water three times.The organic layer was dried over magnesium sulfate, followed by removalof volatile materials and drying, and then recrystallized by usingmethyl chloride and methanol, to thereby obtain 64.0 g of2,9,9-trimethyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one (yield: 94.8%)as white solid.

¹H-NMR (500 MHz, CDCl₃, ppm): δ 1.354-1.369 (d, 3H), 1.517 (s, 6H),2.784-2.811 (d, 2H), 3.444-3.496 (m, 1H), 7.376-7.429 (m, 2H),7.471-7.485 (d, 2H), 7.763 (s, 1H), 7.795-7.808 (d, 2H), 7.832 (s, 1H)

Synthesis of 2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluorene

In a 1000 mL round flask,2,9,9-trimethyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one (50 g, 190.6mmol) was dissolved THF 400 mL and ethanol 400 mL, and then stirred.Sodium borohydride (NaBH₄) (9.4 g, 247.8 mmol) was added to the reactionproduct in five lots, and then stirred for 12 hours. The resultantmixture, after removal of solvent, was dissolved in ethylacetate, andthen washed with water three times. The organic layer was dried overmagnesium sulfate, followed by removal of volatile materials. The driedreaction product was dissolved in 320 mL, of toluene, and then inputtedto a 500 mL round flask. After that, p-toluene sulfonic acid (0.2 g) wasinputted thereto, and then water was completely removed under refluxwith Dean-Stark. The resultant material was cooled to room temperature,and then an aqueous ammonium chloride solution (150 mL) and 200 mL ofdiethyl ether were injected thereto, followed by separation of theorganic layer. The organic layer collected by extracting the residuewith diethyl ether was dried over magnesium sulfate, followed by removalof volatile materials, and then purified by using silica gel columnchromatography, to thereby obtain 42.0 g of2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluorene (yield: 89.42%).

¹H-NMR (500 MHz, CDCl₃, ppm): δ 1.515 (s, 6H), 2.203 (s, 3H), 3.375 (s,2H), 6.559 (s, 1H), 7.279-7.332 (m, 3H), 7.425-7.440 (d, 1H),7.697-7.711 (d, 1H), 7.740 (s, 1H)

Synthesis ofN-tert-butyl-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine

In a 500 mL round flask,2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluorene (15.0 g, 60.9 mmol) wasdissolved in 300 mL of diethyl ether, and then the temperature waslowered to −78° C. Then, n-butyllithium (2.5M hexane solution, 24.8 mL)was slowly injected thereto, followed by stirring at room temperaturefor 12 hours. After volatile materials were removed by vacuum, 350 mL ofn-hexane was added to the mixture to lower the reactor temperature to−78° C., followed by addition of dichlorodimethylsilane (23 g). Thetemperature was again raised to room temperature, followed by stirringfor 24 hours, and then salts were removed through filtering. Then,volatile materials were removed by vacuum. The product was againinputted to a 500 mL round flask, and dissolved in 320 mL of diethylether. The temperature was lowered to −78° C., and tert-butylamine (16.1g, 152.2 mmol) was added thereto. The temperature was raised to roomtemperature, followed by stirring for 12 hours, and then volatilematerials were completely removed by vacuum. Then, 200 mL of toluene wasadded to dissolve the resultant material, and salts were removed throughfiltering. The solvent was removed, to thereby obtain 21.0 g of amixture ofN-tert-butyl-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamine andN-tert-butyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine(yield: 91.8%), as a viscous material.

¹H-NMR (500 MHz, C₆D₆, ppm): δ 0.085-0.098 (d, 6H), 0.229-0.253 (d, 6H),0.555 (s, 2H), 1.161-1.179 (d, 18H), 1.534-1.559 (d, 12H), 2.304 (s,6H), 3.385-3.422 (d, 2H), 6.747 (s, 2H), 7.303-8.049 (m, 12H)

Synthesis of(t-butylamido)dimethyl(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl(Complex 3) and(t-butylamido)dimethyl(2,9,9-trimethyl-1,9-dihydrocyclochloropenta[b]fluoren-1-yl)silanetitanium(IV)dimethyl(Complex 4)

In a 250 mL round flask, a mixture ofN-tert-butyl-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]-fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine(10.4 g, 27.69 mmol) was dissolved in 200 mL of diethyl ether, and thenthe temperature was lowered to −78° C. Then, methyllithium (1.5M diethylether solution, 75.6 mL) was slowly injected thereto. The temperaturewas raised to room temperature, followed by stirring for 12 hours, toprepare lithium salt. In addition, in a dry box, TiCl₄ (5.25 g, 27.69mmol) and 150 mL of anhydrous n-hexane were inputted to a 500 mL roundflask, and then the temperature was lowered to −78° C. Then, theprepared lithium salt was slowly added thereto. Again, the temperaturewas raised to room temperature, followed by stirring for 4 hours, andthen the solvent was removed by vacuum. The resultant material was againdissolved in toluene, and then the undissolved part was removed throughfiltering. Again, toluene was removed by vacuum, to thereby obtain 10.8g of a mixture of Complex 3 and Complex 4, as solid.

¹H-NMR (500 MHz, C₆D₆, ppm): δ −0.019-−0.010 (d, 6H), 0.641-0.647 (d,6H), 0.794-2.212 (m, 48H), 7.004-7.025 (d, 2H), 7.106-8.092 (m, 12H)

Preparation Example 3 Preparation of Mixture of Complex 5 and Complex 6

Synthesis ofN-cyclohexyl-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-cyclohexyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine

In a round flask, 2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluorene (7.5g, 30.5 mmol) was dissolved in 300 mL of diethyl ether, and then thetemperature was lowered to −78° C. Then, n-butyllithium (2.5M hexanesolution, 12.4 mL) was slowly injected thereto, followed by stirring atroom temperature for 12 hours. After the volatile materials were removedby vacuum, 200 mL of n-hexane was added to the mixture to lower thereactor temperature to −78° C., followed by addition ofdichlorodimethylsilane (11.8 g, 91.4 mmol). The temperature was againraised to room temperature, followed by stirring for 24 hours, and thensalts were removed through filtering. Then, volatile materials wereremoved by vacuum. The product was again inputted to a 200 mL roundflask, and dissolved in 150 mL of diethyl ether. The temperature waslowered to −78° C., and cyclohexaneamine (9.05 g, 91.4 mmol) was addedthereto. The temperature was raised to room temperature, followed bystirring for 12 hours, and then volatile materials were completelyremoved by vacuum. Then, 100 mL of toluene was added to dissolve theresultant material, and salts were removed through filtering. Thesolvent was removed, to thereby obtain 10.6 g of a mixture ofN-cyclohexyl-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-cyclohexyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine,as viscous material.

Synthesis of(cyclohexylamido)dimethyl(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl(Complex 5) and(cyclohexylamido)dimethyl(2,9,9-trimethyl-1,9-dihydrocyclochloropenta[b]fluoren-1-yl)silanetitanium(IV)dimethyl(Complex 6)

In a 250 mL of three-neck round flask, the well-dried mixture ofN-cyclohexyl-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-cyclohexyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine(10.6 g, 26.39 mmol) was dissolved in 200 mL of diethyl ether, and thenthe temperature was lowered to −78° C. Then, methyllithium (1.5M diethylether solution, 72.1 mL) was slowly injected thereto. The temperaturewas raised to room temperature, followed by stirring for 12 hours, toprepare lithium salt. In addition, in a dry box, TiCl₄ (5.00 g, 26.39mmol) and 150 mL of anhydrous n-hexane were inputted to a 500 mL roundflask, and then the temperature was lowered to −78° C. Then, theprepared lithium salt was slowly added thereto. Again, the temperaturewas raised to room temperature, followed by stirring for 4 hours, andthen the solvent was removed by vacuum. The resultant material was againdissolved in toluene, and then the undissolved part was removed throughfiltering. Again, toluene was removed by vacuum, to thereby obtain 11.5g of a mixture of Complex 5 and Complex 6, as solid.

¹H-NMR (500 MHz, C₆D₆, ppm): δ −0.070-−0.049 (d, 6H), 0.628-0.634 (d,6H), 0.764-2.195 (m, 50H), 4.779 (m, 2H), 6.985-7.002 (d, 2H),7.100-8.095 (m, 12H)

Preparation Example 4 Preparation of Mixture of Complex 7 and Complex 8

Synthesis of 9,9-ditetradecyl-9H-fluorene

A 2000 mL round flask was charged with 9H-fluorene (15 g, 90.24 mmol)and potassium tert-butoxide (21.2 g, 198.5 mmol), and then 300 mL ofDMSO was slowly injected thereto. Under nitrogen atmosphere,1-bromotetradecane (54 g, 198.5 mmol) was slowly dropped through adropping funnel while the reactor temperature was maintained at 10° C.or lower. The mixture was stirred at room temperature for 24 hours, andthe reaction was terminated by addition of 500 mL of distilled water.The organic layer collected by extraction with n-hexane was dried overmagnesium sulfate, followed by removal of volatile materials, and thenpurified with n-hexane by using silica gel column chromatography tube,followed by drying, to thereby obtain 42.0 g of9,9-ditetradecyl-9H-fluorene (yield: 83.26%) as white solid.

¹H-NMR (500 MHz, CDCl₃, ppm): δ 0.616-0.634 (m, 4H), 0.881-0.909 (m,6H), 1.051-1.323 (m, 44H), 1.951-1.984 (t, 4H), 7.292-7.355 (m, 6H),7.708-7.722 (d, 2H)

Synthesis of2-methyl-9,9-ditetradecyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one

A 5000 mL round flask was charged with 9,9-ditetradecyl-9H-fluorene (30g, 53.7 mmol) and 2-bromo-2-methylpropanoyl bromide (12.7 g, 55.3 mmol),and then dissolved with 300 mL of carbon disulfide inputted thereto.Then, the reactor was cooled with ice water. Under nitrogen atmosphere,aluminum trichloride (15.7 g, 118.1 mmol) was slowly added thereto inten lots over 2 hours. The mixture was stirred at room temperature for 8hours, and then the reaction was terminated by addition of 100 mL ofdistilled water, followed by washing with 500 mL of distilled waterthree times. The organic layer was dried over magnesium sulfate,followed by removal of volatile materials and drying, to thereby obtain30.0 g of2-methyl-9,9-ditetradecyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one(yield: 89.1%) as highly viscous oil.

¹H-NMR (500 MHz, CDCl₃, ppm): δ 0.590 (m, 4H), 0.867-0.895 (m, 6H),1.024-1.295 (m, 44H), 1.367-1.382 (d, 3H), 1.963-2.204 (t, 4H),2.792-2.826 (d, 2H), 3.448-3.500 (m, 1H), 7.372-7.400 (m, 3H),7.726-7.780 (m, 3H)

Synthesis of 2-methyl-9,9-ditetradecyl-3,9-dihydrocyclopenta[b]fluorene

In a 500 mL round flask, 2methyl-9,9-ditetradecyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one (20 g,31.9 mmol) was dissolved in 150 mL of THF and 150 mL of ethanol, andthen stirred. Sodium borohydride (NaBH₄) (1.8 g, 47.8 mmol) was added tothe reactant in five lots, and then stirred for 12 hours. The resultantmixture, after removal of solvent, was dissolved in ethylacetate, andthen washed with water three times. The organic layer was dried overmagnesium sulfate, followed by removal of volatile materials. The driedreactant was dissolved in 150 mL of toluene, and then inputted to around flask. After that, p-toluene sulfonic acid (0.08 g) was inputtedthereto, and then water was completely removed under reflux withDean-Stark. The resultant material was cooled to room temperature, andthen an aqueous ammonium chloride solution (100 mL) and 200 mL ofdiethyl ether were injected thereto, followed by separation of theorganic layer. The organic layer collected by extracting the residuewith diethyl ether was dried over magnesium sulfate, followed by removalof volatile materials, and then purified by using silica gel columnchromatography, to thereby obtain 15.3 g of 2methyl-9,9-ditetradecyl-3,9-dihydrocyclopenta[b]fluorene (yield: 78.5%).

¹H-NMR (500 MHz, CDCl₃, ppm): δ 0.649-0.665 (m, 4H), 0.891-0.918 (m,6H), 1.059-1.319 (m, 44H), 1.953-1.986 (t, 4H), 2.206 (s, 3H), 3.378 (s,2H), 6.562 (s, 1H), 7.237-7.332 (m, 4H), 7.663-7.678 (d, 1H), 7.710 (s,1H)

Synthesis ofN-tert-butyl-1-(9,9-ditetradecyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(9,9-ditetradecyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine

In a 250 mL round flask,2-methyl-9,9-ditetradecyl-3,9-dihydrocyclopenta[b]fluorene (4.9 g, 8.0mmol) was dissolved in 100 mL of anhydrous diethyl ether, and then thetemperature was lowered to −78° C. Then, n-butyllithium (1.6M hexanesolution, 5.5 mL) was slowly injected thereto, followed by stirring atroom temperature for 12 hours. After volatile materials were removed byvacuum, 100 mL of n-hexane was added to the mixture to lower the reactortemperature to −78° C., followed by addition of dichlorodimethylsilane(2.9 g). The temperature was again raised to room temperature, followedby stirring for 24 hours, and then salts were removed through filtering.Then, volatile materials were removed by vacuum. The product was againinputted to a 250 mL round flask, and dissolved in 100 mL of diethylether. The temperature was lowered to −78° C., and tert-butylamine (1.8g, 24.1 mmol) was added thereto. The temperature was raised to roomtemperature, followed by stirring for 12 hours, and then volatilematerials were completely removed by vacuum. Then, 200 mL of n-hexanewas added to dissolve the resultant material, and salts were removedthrough filtering. The solvent was removed, to thereby obtain 5.5 g of amixture ofN-tert-butyl-1-(9,9-ditetradecyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(9,9-ditetradecyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine(ratio=˜1:1), (yield: 92.7%), as high viscous material.

¹H-NMR (500 MHz, C₆D₆, ppm): δ 0.145 (s, 3H), 0.183-0.204 (d, 6H), 0.290(s, 3H), 0.552 (s, 1H), 0.603 (s, 1H), 0.998-1.370 (m, 126H),2.228-2.301 (m, 14H), 3.408-3.435 (d, 2H), 6.749-6.760 (d, 2H),7.353-7.461 (m, 6H), 7.546-8.073 (m, 6H)

Synthesis of(t-butylamido)dimethyl(9,9-ditetradecyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl(Complex 7) and(t-butylamido)dimethyl(9,9-ditetradecyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)silanetitanium(IV)dimethyl (Complex 8)

In a 250 mL round flask, a mixture ofN-tert-butyl-1-(9,9-ditetradecyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(9,9-ditetradecyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine(ratio=˜1:1) (5.0 g, 6.8 mmol) was dissolved in 100 mL of diethyl ether,and then the temperature was lowered to −78° C. Then, methyllithium(1.5M diethyl ether solution, 18.5 mL) was slowly injected thereto. Thetemperature was raised to room temperature, followed by stirring for 12hours, to prepare lithium salt. In addition, in a dry box, TiCl₄ (16.75mmol) and 50 mL of anhydrous n-hexane were inputted to a 250 mL roundflask, and then the temperature was lowered to −78° C. Then, theprepared lithium salt was slowly added thereto. The temperature wasagain raised to room temperature, followed by stirring for 4 hours, andthe solvent was removed by vacuum. The resultant material was dissolvedin n-hexane, and then the filtrate was extracted through filtering.Again, n-hexane was removed by vacuum, to thereby obtain 5.2 g of amixture of Complex 7 and Complex 8 (ratio of approximately 1:1), assolid.

¹H-NMR (500 MHz, C₆D₆, ppm): δ 0.093-0.104 (d, 6H), 0.630-0.647 (d, 6H),0.856-1.392 (m, 120H), 1.609-1.643 (d, 18H), 2.095-2.214 (m, 14H),7.023-7.041 (d, 2H), 7.305-8.097 (m, 12H)

Comparative Preparation Example 1 Preparation of(t-butylamido)dimethyl(2-methylindenyl)silanetitanium(IV)dimethyl

It was prepared starting from 2-methylindene by a synthesizing methoddisclosed in the reference “Journal of Organometallic Chemistry 666(2002) 5-26”.

Preparation of EPDM Example 1-Example 8 Preparation of EPDM byContinuous Solution Polymerization Process

Ethylene, propylene, and 5-ethylidene-2-norbornene (ENB) werepolymerized through the catalyst prepared in the present invention byusing a continuous type polymerization apparatus, to thereby prepareEPDM. The catalysts synthesized in Preparation Examples 1 to 4 andComparative Preparation Example 1 were used as single activation pointcatalysts, and cyclohexane was used as the solvent. The amounts ofcatalysts used are described in Table 1 below. Ti, Al, and B indicate asingle activation point catalyst, triisobutyl aluminum as a cocatalyst,and triphenylmethyl tetrakis(pentafluorophenyl)borate, respectively. Therespective catalysts were injected while they each were dissolved intoluene in a concentration of 0.2 g/l, and the synthesis was carried outby using propylene as an α-olefin comonomer and5-ethylidene-2-norbornene (ENB) as a diene monomer. The conversion ratioof the reactor may be estimated through reaction conditions andtemperature gradient in the reactor when one kind of polymer wasprepared by polymerization in the respective reaction conditions. Themolecular weight, in the case of a single activation point catalyst, wascontrolled as a function of the reactor temperature, conversion ratio,and hydrogen content, and detailed polymerization conditions andpolymerization results are shown in Table 1 below.

TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6Polymerization Catalyst Preparation Preparation Preparation PreparationPreparation Preparation conditions Example 1 Example 1 Example 1 Example2 Example 2 Example 2 Total solution flux 5 5 5 5 5 5 (kg/h) Feedingamount of 5 5 5 5 5 5 ethylene (wt %) Feeding weight 1/1.5/0.3 1/1/0.31/0.7/0.3 1/1.5/0.3 1/1/0.3 1/0.7/0.3 ratio of monomer (C2/C3/ENB)Feeding amount 7 7 7 10 10 10 of Ti (μmol/kg) Al/Ti ratio 70 70 70 50 5050 B/Ti ratio 2.5 2.5 2.5 2.5 2.5 2.5 Reaction 120 120 120 100 100 100Temperature (° C.) Polymerization C2 weight % 57.74 64.89 71.53 51.6659.39 66.02 results ENB 7.1 8.1 8.9 9.5 10.1 10.5 weight % C2 conversion66.7 66.3 69.2 90.0 84.3 81.7 ratio (%) Mooney Viscosity 30.6 52.4 76.270.7 109.6 141.6 (@125° C.) Comparative Comparative Comparative Example7 Example 8 Example 1 Example 2 Example 3 Polymerization CatalystPreparation Preparation Comparative Comparative Comparative conditionsExample 3 Example 4 Preparation Preparation Preparation Example 1Example 1 Example 1 Total solution flux 5 5 5 5 5 (kg/h) Feeding amountof 5 5 5 5 5 ethylene (wt %) Feeding weight 1/1/0.3 1/0.7/0.3 1/1.5/0.31/1/0.3 1/0.7/0.3 ratio of monomer (C2/C3/ENB) Feeding amount 10 7 15 1515 of Ti (μmol/kg) Al/Ti ratio 50 50 35 35 35 B/Ti ratio 2.5 2.5 2.5 2.52.5 Reaction 90 120 120 120 120 Temperature (° C.) Polymerization C2weight % 57.6 69.6 56.53 65.08 64.78 results ENB 7.85 9.82 5.0 5.2 5.2weight % C2 conversion 44.0 80.5 46.4 50.1 52.6 ratio (%) MooneyViscosity 34.1 28.0 17.6 16.2 16.7 (@125° C.) Ti: Ti in the singleactivation point catalyst Al: Triisobutylaluminum as cocatalyst B:Triphenylmethyl tetrakis(pentafluorophenyl)borate as cocatalyst.

It can be seen from Table 1 above that, in Examples 1 to 8 prepared byusing the catalyst developed in the present invention, EPDM productsallowing easy injection of comonomers (C3 and ENB) and having a highconversion ratio and high Mooney viscosity can be prepared even underthe high-temperature polymerization conditions. Therefore, it can beconfirmed that an EPDM polymerization system using the single activationpoint catalyst developed in the present invention is a more economicalcatalyst system than the EPDM polymerization system using the existingsingle activation catalyst due to easy control of physical properties(molecular weight and composition of comonomer) of products and highactivity.

The present invention has been described in detail with reference toexamples as set forth above, but those skilled in the art to which theinvention pertains can make various modifications without departing fromthe spirit and scope of the invention defined in appended claims.Therefore, alterations and modifications of the examples of the presentinvention would not depart from the technique of the present invention.

INDUSTRIAL APPLICABILITY

As set forth above, in the method of preparing theethylene-α-olefin-diene copolymer according to the present invention,the transition metal compound based on a cyclopenta[b]fluorenyl group isused as a polymerization catalyst, and thus, ethylene-α-olefin-dienecopolymers having a high diene content, a high conversion ratio, andhigh Mooney viscosity can be prepared under the high-temperature (120°C. or higher) polymerization conditions at a high yield. Further, thecatalyst composition containing the transition metal compound can beeasily prepared at a high synthesis yield in an economical manner.Further, the transition metal compound or the catalyst compositionaccording to the present invention can have excellent copolymerizationreactivity with other olefins while maintaining high catalytic activityeven at high temperature due to excellent thermal stability thereof andallow the preparation of high-molecular weight polymers at a high yield,resulting in higher commercial practicability as compared with thealready known metallocene and non-metallocene based single activationpoint catalysts.

The invention claimed is:
 1. A method of preparing anethylene-α-olefin-diene copolymer by using a transition metal catalystcomposition including a transition metal compound represented byChemical Formula 1 below:

In Chemical Formula 1, M is a Group 4 transition metal in the PeriodicTable of Elements; n is an integer of 1 or 2, each R₁ may be the same ordifferent when n is 2; R₁ is hydrogen, (C1-C50)alkyl, halo(C1-C50)alkyl,(C3-C50)cycloalkyl, (C6-C30)aryl, (C6-C30)aryl(C1-C50)alkyl,((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl, —NR^(a)R^(b),—SiR^(c)R^(d)R^(e), or 5- through 7-membered N-heterocycloalkylcontaining at least one nitrogen atom; R₂ and R₃ each are independentlyhydrogen, (C1-C50)alkyl, (C1-C50)alkoxy, halo(C1-C50)alkyl,(C3-C50)cycloalkyl, (C6-C30)aryl, (C6-C30)aryloxy,(C1-C50)alkyl(C6-C30)aryloxy, (C6-C30)aryl(C1-C50)alkyl,((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl, —NR^(a)R^(b) or—Si^(c)R^(d)R^(e); R₄, R₅, R₁₀, R₁₁ and R₁₂ each are independently(C1-C50)alkyl, halo(C1-C50)alkyl, (C3-C50)cycloalkyl, (C6-C30)aryl,(C6-C30)aryl(C1-C50)alkyl, ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl,—NR^(a)R^(b), or —SiR^(c)R^(d)R^(e), and R₁₁ and R₁₂ are optionallylinked via (C4-C7)alkylene to form a ring; R₆, R₇, R₈ and R₉ each areindependently hydrogen, (C1-C50)alkyl, halo(C1-C50)alkyl,(C3-C50)cycloalkyl, (C1-C50)alkoxy, (C6-C30)aryl,(C6-C30)aryl(C1-C50)alkyl, ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl,(C6-C30)aryloxy, (C1-C50)alkyl(C6-C30)aryloxy, N-carbazolyl,—NR^(a)R^(b), or —SiR^(c)R^(d)R^(e), or are optionally linked to anadjacent substituent via (C1-C5)alkylene to form a ring, and at leastone —CH₂— of the alkylene is optionally substituted by a hetero atomselected from —O—, —S—, and —NR′—, and the alkylene is optionallyfurther substituted with (C1-C50)alkyl; aryl of R₁ to R₁₂ is optionallyfurther substituted with at least one substituent selected from thegroup consisting of (C1-C50)alkyl, halo(C1-C50)alkyl, (C1-C50)alkoxy,(C6-C30)aryloxy, (C6-C30)aryl, (C1-C50)alkyl(C6-C30)aryl, and(C6-C30)aryl(C1-C50)alkyl; R′ and R^(a) to R^(e) each are independently(C1-C50)alkyl or (C6-C30)aryl; and X₁ and X₂ each are independentlyhalogen, (C1-C50)alkyl, (C2-C50)alkenyl, (C3-C50)cycloalkyl,(C6-C30)aryl, (C6-C30)aryl(C1-C50)alkyl,((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl, (C1-C50)alkoxy,(C6-C30)aryloxy, (C1-C50)alkyl(C6-C30)aryloxy,(C1-C50)alkoxy(C6-C30)aryloxy, (C1-C50)alkylidene, or an anion ordianion ligand consisting of 60 or less atoms containing N, P, O, S, Si,and halogen, except hydrogen, provided that one of X₁ and X₂ is adianion ligand, the other is ignored.
 2. The method of claim 1, whereinthe transition metal compound is represented by Chemical Formula 2 or 3below:

In Chemical Formulas 2 and 3, M, R₂ to R₁₂, X₁ and X₂ have the samedefinition in Chemical Formula 1 of claim 1; R₂₁ and R₂₂ each areindependently hydrogen, (C1-C50)alkyl, halo(C1-C50)alkyl,(C3-C50)cycloalkyl, (C6-C30)aryl, (C6-C30)aryl(C1-C50)alkyl,((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl, —NR^(a)R^(b),—SiR^(c)R^(d)R^(e), or 5- through 7-membered N-heterocycloalkylcontaining at least one nitrogen atom; aryls of R₂₁ and R₂₂ areoptionally further substituted with at least one substituent selectedfrom the group consisting of halogen, (C1-C50)alkyl, halo(C1-C50)alkyl,(C1-C50)alkoxy, (C6-C30)aryloxy, (C6-C30)aryl,(C1-C50)alkyl(C6-C30)aryl, and (C6-C30)aryl(C1-C50)alkyl; and R^(a) toR^(e) each are independently (C1-C50)alkyl or (C6-C30)aryl.
 3. Themethod of claim 2, wherein the transition metal compound is selectedfrom the compounds below:


4. The method of claim 1, wherein the transition metal catalystcomposition further includes a cocatalyst selected from an aluminumcompound, a boron compound, or a mixture thereof.
 5. The method of claim4, wherein the transition metal compound and the cocatalyst have a molarratio of transition metal (M):boron atom (B):aluminum atom (Al) in therange of 1:0˜100:1˜2,000.
 6. The method of claim 5, wherein thetransition metal compound and the cocatalyst have a molar ratio oftransition metal (M):boron atom (B):aluminum atom (Al) in the range of1:0.5˜5:10˜500.
 7. The method of claim 1, wherein the α-olefin monomeris at least one selected from the group consisting of propylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene,1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, cyclopentene, cyclohexene, norbornene, phenylnorbornene,styrene, α-methylstyrene, p-methylstyrene, and 3-chloromethylstyrene;and the diene monomer is at least one selected from 1,3-butadiene,1,4-pentadiene, 2-methyl-1,3-butadiene, 1,4-hexadiene, 1,5-hexadiene,1,5-heptadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene,1,7-nonadiene, 1,8-nonadiene, 1,8-decadiene, 1,9-decadiene,1,12-tetradecadiene, 1,13-tetradecadiene, 3-methyl-1,4-hexadiene,3-methyl-1,5-hexadiene, 3-ethyl-1,4-hexadiene, 3-ethyl-1,5-hexadiene,3,3-dimethyl-1,4-hexadiene, 3,3-dimethyl-1,5-hexadiene, cyclopentadiene,cyclohexadiene, 5-vinyl-2-norbornene, 2,5-norbornadiene,7-methyl-2,5-norbornadiene, 7-ethyl-2,5-norbornadiene,7-propyl-2,5-norbornadiene, 7-butyl-2,5-norbornadiene,7-phenyl-2,5-norbornadiene, 7-hexyl-2,5-norbornadiene,7,7-dimethyl-2,5-norbornadiene, 7-methyl-7-ethyl-2,5-norbornadiene,7-chloro-2,5-norbornadiene, 7-bromo-2,5-norbornadiene,7-fluoro-2,5-norbornadiene, 7,7-dichloro-2,5-norbornadiene,1-methyl-2,5-norbornadiene, 1-ethyl-2,5-norbornadiene,1-propyl-2,5-norbornadiene, 1-butyl-2,5-norbornadiene,1-chloro-2,5-norbornadiene, 1-bromo-2,5-norbornadiene,5-isopropyl-2-norbornene, 5-vinylidene-2-norbornene (VNB),5-methylene-2-norbornene (MNB), and 5-ethylidene-2-norbornene (ENB). 8.The method of claim 1, wherein the ethylene-α-olefin-diene copolymercontains 30 to 85 wt % of ethylene, 1 to 15 wt % of diene, and the restof α-olefin.
 9. The method of claim 7, wherein a pressure in a reactorfor copolymerization of ethylene monomers, α-olefin monomers, and dienemonomers is 1˜1000 atm, and a polymerization reaction temperature is25˜200° C.
 10. The method of claim 9, wherein at the time of preparingthe ethylene-α-olefin-diene copolymer, the pressure in the reactor is6˜150 atm, and the polymerization reaction temperature is 50˜180° C. 11.The method of claim 1, wherein the ethylene-α-olefin-diene copolymer hasMooney viscosity (ASTM D1646-94, ML1+4@125° C.) of 1 to
 250. 12. Themethod of claim 11, wherein the ethylene-α-olefin-diene copolymer hasMooney viscosity (ASTM D1646-94, ML1+4@125° C.) of 10 to 200.